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PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
21
pubmed:dateCreated
2009-10-27
pubmed:abstractText
The ability to chemically wire ionomer films to electrode surfaces can promote transport near interfaces and impact a host of energy-related applications. Here, we demonstrate proof-of-concept principles for the surface-initiated ring-opening metathesis polymerization (SI-ROMP) of norbornene (NB), 5-butylnorbornene (NBH4), and 5-perfluorobutylnorbornene (NBF4) from Pt-modified gold substrates and the subsequent sulfonation of olefins along the polymer backbones to produce ultrathin sulfonated polymer films. Prior to sulfonation, the films are hydrophobic and exhibit large barriers against ion transport, but sulfonation dramatically reduces the resistance of the films by providing pathways for proton diffusion. Sulfonated films derived from NBF4 and NBH4 yield more anodic potentials for oxygen reduction than those derived from NB or unfunctionalized electrodes. These improvements are consistent with hydrophobic structuring by the fluorocarbon or hydrocarbon side groups to minimize interfacial flooding and generate pathways for enhanced O(2) permeation near the interface. Importantly, we demonstrate that the sulfonated polymer chains remain anchored to the surface during voltammetry for oxygen reduction whereas short-chain thiolates that do not tether polymer are removed from the substrate. This approach, which we extend to unmodified gold electrodes at neutral pH, presents a method of cleaning the ionomer/electrode interface to remove molecular components that may hamper the performance of the electrode.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
Nov
pubmed:issn
1520-5827
pubmed:author
pubmed:issnType
Electronic
pubmed:day
3
pubmed:volume
25
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
12721-8
pubmed:year
2009
pubmed:articleTitle
Surface-initiated growth of ionomer films from pt-modified gold electrodes.
pubmed:affiliation
Department of Chemical and Biomolecular Engineering, Vanderbilt University, Nashville, Tennessee 37235, USA.
pubmed:publicationType
Journal Article